Disperse dyes

ABSTRACT

Disperse dyes of the general formula (I)  
                 
where 
 
D is a diazo component derived from a substituted or unsubstituted aromatic amine, K is an aromatic radical of the formula  
                 
and the substituents are each as defined in the first claim. Further described are the preparation and the use of the dyes according to the invention.

The invention relates to disperse dyes of the general formula (I)

where

D is a diazo component derived from a substituted or unsubstitutedaromatic amine,

K is an aromatic radical of the formula K,, K₂ or K₃

R₁ is hydrogen, chlorine, C₁₋₂-alkyl, C₁₋₂-alkoxy, hydroxyl oracylamino, R₂ is hydrogen, C₁-alkoxy, C₁₋₂-alkoxyethoxy, chlorine,bromine or combines with R₃ to form a group of the formula—*CH(CH₃)CH₂C(CH₃)₂— (* attached to the nucleus),

R₃ is hydrogen, C₁₋₆alkyl, C₃₋₄-alkenyl, chloro- or bromo-C₃₋₄-alkenyl,C₃₋₄-alkynyl, phenyl-C₁₋₃-alkyl, C₁₋₄-alkoxycarbonyl-C₁₋₃-alkyl,C₃₋₄-alkenyloxycarbonyl-C₁₋₃-alkyl, C₃₋₄-alkynyloxycarbonyl-C₁₋₃-alkyl,phenoxy-C₂₋₄-alkyl, halogen-, cyano-, C₁₋₄-alkoxy-,C₁₋₄-alkylcarbonyloxy- or C₁₋₄-alkoxycarbonyloxy-substituted C₂₋₄-alkyl,or a group of the formula —CH₂—CH(R₈)CH₂—R₉,

R₄ is hydrogen or C₁₋₂-alkyl,

R₅ is phenyl which may be substituted by one or two substituentsselected from the group consisting of methyl, chlorine, bromine andnitro or combines with R₄ to form a c-pentanone or c-hexanone ring,

R₆ is hydrogen or hydroxyl,

R₇ is hydrogen or methyl,

R₈ is hydroxyl or ₁₋₄-alkylcarbonyloxy,

R₉ is chlorine, C₁₋₄-alkoxy, phenoxy, allyloxy or C₁₋₄-alkylcarbonyloxy,

Y is C₁₋₃-alkylene,

wherein R₃ is just hydrogen when K is a radical of the formula K₂ or K₃.

Excluded from the invention is the dye compound of the formula

as disclosed in example 29 of WO 2004/035690 A1.

A group of preferred dyes of the formula I conform to the generalformula (Ia)

where

D₁ is 3-phenyl-1,2,4-thiadiazolyl or conforms to one of the followingformulae:

where

(a) is hydrogen, chlorine, bromine, cyano, nitro-, C₁₋₄-alkoxycarbonyl,C₁₋₃-alkyl-sulphonyl, preferably hydrogen, chlorine, cyano or nitro,

(b) is chlorine, bromine, nitro, methyl, C₁₋₂-alkylsulphonyl,C₁₋₄-alkylcarbonyl, aminosulphonyl, mono- ordi-C₁₋₄-alkylaminosulphonyl, phenylaminosulphonyl, C₁₋₄-alkoxycarbonyl,benzyloxycarbonyl, tetrahydrofurfuryl-2-oxycarbonyl,C₃₋₄-alkenyloxycarbonyl, C₃₋₄-alkynyloxycarbonyl, aminocarbonyl, mono-or di-C₁₋₄-alkylaminocarbonyl, phenylaminocarbonyl or phenylazo,

(c) is hydrogen or chlorine or else (when d is hydrogen) hydroxyl orrhodan,

(d) is hydrogen, chlorine, bromine, hydroxyl or cyano,

(e) is nitro, C₁₋₄-alkylcarbonyl, C₁₋₄-alkoxycarbonyl, cyano,aminocarbonyl, mono- or di-C₁₋₄-alkylaminocarbonyl,

(f) is hydrogen, chlorine, bromine, C₁₋₂-alkyl or phenyl,

(g) is nitro, cyano, formyl, dicyanovinyl or a group of the formula—CH═CH—NO₂, —CH═C(CN)CO—OC₁₋₄-alkyl, H₅C₆—N═N— or 3- or 4—NO₂—C₆H₄—N═N—,

(h) is cyano or C₁₋₄-alkoxycarbonyl,

(i) is C₁₋₄-alkyl or phenyl,

(j) is —CN, —CH═CH₂ or phenyl,

(k) is C₁₋₄-alkyl,

(l) is hydrogen, chlorine, bromine, cyano, rhodan, nitro,C₁₋₄-alkoxycarbonyl or di-C₁₋₄-alkylaminosulphonyl,

(p) is hydrogen, chlorine or bromine, and

(q) is C₁₋₄-alkyl or C₁₋₄-alkoxycarbonyl-C₁₋₄-alkyl, wherein the phenylnuclei of these substituents may bear one or two substituents selectedfrom the group consisting of chlorine, bromine, methyl and C₁₋₂-alkoxy,

R′₁ is hydrogen, methyl, chlorine or acylamino,

R′₂ is hydrogen, chlorine, C₁₋₂-alkoxy, C₁₋₂-alkoxyethoxy or combineswith R₃ to form a group of the formula —CH(CH₃)CH₂C(CH₃)₂—,

R₃ and R₅ are each as defined above,

R′₄ is hydrogen or methyl, and

Y is a group of the formula —CH₂CH₂— or —CH₂CH(CH₃)—.

Particular preference is given to disperse dyes of the formula (Ib)

where

D₂ is the residue of a diazo component of the formula2,6-dicyano-4-chloro-, 2,6-dicyano-4-bromo-, 2,6-dicyano-4-methyl-,2,6-dicyano-4-nitrophenyl, 2,4-dinitro-6-chloro-, 2,4-dinitro-6-bromo-or 2,4-dinitro-6-cyanophenyl, 2-chloro-4-nitro-6-cyanophenyl,2-bromo-4-nitro-6-cyanophenyl, 2,4-dinitrophenyl,2,6-dichloro-4-nitrophenyl, 2,6-dibromo-4-nitrophenyl,2-chloro-4-nitro-6-bromophenyl, 2-chloro-4-nitrophenyl,2-cyano-4-nitrophenyl, 2,4-dinitro-5,6-dichlorophenyl,2,5-dichloro-4-nitrophenyl, 4-nitro-phenyl, 4-phenylazophenyl,4—C₁₋₄-alkoxycarbonylphenyl, 2-C₁₋₄-alkoxy-carbonyl-4-nitrophenyl,4-benzyloxycarbonylphenyl, 4-(tetrahydrofurfuryl-2′-oxycarbonyl)phenyl,3,5-dicyano-4-chloro-thienyl-2,3,5-dicyano-thienyl-2,3-cyano-5-nitro-thienyl-2,3-acetyl-5-nitro-thienyl-2,3,5-dinitro-thienyl-2,3-(C₁₋₄-alkoxycarbonyl)-5-nitro-thienyl-2,5-phenylazo-3-cyano-thienyl-2, 5-phenylazo-3-cyano-4-methyl-thienyl-2,5-nitro-thiazolyl-2, 5-nitrobenzoiso-thiazolyl-3,3-methyl-4-cyano-isothiazolyl-5, 3-phenyl-1,2,4-thiadiazolyl-2, 5-(C₁₂-alkylmercapto)-1,3,4-thiadiazolyl-2,3-(C₁₋₂-alkoxycarbonylethyl-mercapto)-1,2,4-thiadiazolyl-5,1-cyanomethyl-4,5-dicyano-imidazolyl-2, 6-nitrobenzothiazolyl-2,5-nitrobenzothiazolyl-2, 6-rhodanbenzothiazolyl-2,6-chlorobenzothiazolyl-2, (5),6,(7)-dichlorobenzothiazolyl-2, or of theformula

and B is oxygen or a group of the formula ═(CN)₂, ═CH—NO₂,═(CN)—COOC₁₋₄alkyl or ═(CN)—COOC₃₋₄alkenyl

and the symbols R′₁, R′₂, R₃, R′₄, R₅ and Y are each as defined above.

Particular preference is further given to the disperse dyes of theformula I where

D is a diazo component selected from the group consisting of2,4-dinitro-6-chloro-phenyl, 2,4-dinitro-6-bromophenyl,2,4-dinitro-6-cyanophenyl or 2,6-dicyano4-nitrophenyl,

K is a radical of the formula K₁,

R₁ is C₁₋₂₋alkylcarbonylamino with or without bromine, chlorine,hydroxyl or C₁₋₂-alkoxy substitution; phenylaminocarbonyl,methylsulphonylamino, methyl or hydrogen,

R₂ is C₁₋₂₋alkoxy or hydrogen,

R₃ is hydrogen, C₁₋₄-alkyl, cyanoethyl, C₁₋₂-alkoxyethyl or C₃₋₄-alkenyl

R₄ is hydrogen,

R₅ is phenyl, and

Y is a group of the formula —CH₂CH₂—.

Useful diazo components include all mono- to binuclear carbo- orheterocyclic organic radicals or residues of aromatic character whichcan bear customary disperse dye substituents except in particularwater-solubilizing substituents, i.e. sulphonic acid groups especially.Useful diazo components further include residues of monoazo compounds.Examples of diazo components are: preferably substituted phenyl,thienyl, thiazolyl, isothiazolyl, thiadiazolyl, pyrazolyl, imidazolyl,triazolyl, benzothiazolyl or benzisothiazolyl radicals.

All the alkyl groups mentioned contain, unless otherwise stated, 1 to 8and especially 1 to 4 carbon atoms, they can be straight-chain orbranched and may be substituted, for example by halogen atoms,preferably bromine or chlorine atoms, hydroxyl, alkoxy, phenyl, phenoxy,cyano, rhodan, acyl, acyloxy or acylamino groups.

The Y interlink is preferably a group of the formula —CH₂CH₂— or—CH₂CH(CH₃)— especially —CH₂CH₂—.

All alkyl, alkylene and alkenyl radicals are straight chain, unlessstated otherwise.

The process for preparing the novel dyes of the formula (I) ischaracterized in that a diazotized amine of the formula (II)D—NH₂   (II)

is coupled with a compound of the formula (III)H—K   (III).

Diazotizing and coupling are carried out according to commonly knownmethods.

The compounds of the formulae II and III are known or are easy toprepare from known compounds by methods known to one skilled in the art.

The novel dyes of the formula (I) exhibit excellent exhaustion from anaqueous suspension onto textile material composed of manufacturedsynthetic or natural polymer hydrophobic macromolecular organicsubstances. They are particularly useful for dyeing or printing textilematerial composed of linear aromatic polyesters and also of celluloseacetate and cellulose triacetate.

Dyeing or printing is accomplished by processes known per se, forexample those described in French patent 1 445 371.

The dyeings obtained have good allround fastnesses; worth emphasizingare the light fastness, the fastness to dry heat setting and coating andalso the excellent wet fastnesses, after thermal stabilization(thermomigration fastness).

The formulae (I) dyes used according to the invention can be used fordyeing and printing manufactured natural polymer and especiallysynthetic hydrophobic fibre materials, in particular textile materials.Textile materials composed of blend fabrics comprising such manufacturednatural polymer or synthetic hydrophobic fibre materials are likewisedyeable or printable with the dyes of the formula (I).

Useful manufactured natural polymer hydrophobic textile materialsinclude for example acetate filament (cellulose acetate) and cellulosetriacetate.

Synthetic hydrophobic textile materials consist for example of lineararomatic polyesters, for example polyesters from terephthalic acid andglycols, particularly ethylene glycol, or condensation products ofterephthalic acid and 1,4-bis-(hydroxymethyl)-cyclohexane; ofpolycarbonates, for example those formed from alpha,alpha-dimethyl-4,4′-dihydroxydiphenylmethane and phosgene, of fibresbased on polyvinyl chloride and especially on polyamide.

The textile material mentioned may be present at dyeing or printing inthe various processing forms, for example as fibre, yarn or web, as awoven or loop-formingly knitted fabric or in the form of carpets.

The dyes of the formula (I) are applied to the textile materials byknown dyeing processes. For example, polyester fibre materials areexhaust dyed from an aqueous dispersion in the presence of customaryanionic or nonionic dispersants with or without customary carriers attemperatures between 80 and 140° C. Cellulose acetate is preferably dyedat between about 65 to 85° C. and cellulose triacetate at temperaturesof up to 115° C.

Polyamide-based fibre materials are preferably dyed at a pH of 3 to 7and especially 3 to 5. The dyeing is preferably carried out at atemperature of 70 to 110° C. and especially 80 to 105° C.

The liquor ratio depends on the apparatus, the substrate and the make-upform. How

ever, the liquor ratio can be chosen within a wide range, for examplefrom 4:1 to 100:1, but preferably 5:1 to 30:1.

The formula (I) dyes used according to the invention can be applied inthe customary dyeing processes, such as for example in the exhaustprocess, continuous process or printing process.

The formula (I) dyes used according to the invention are also useful fordyeing from short liquors, for example in continuous dyeing processes orbatch and continuous foam dyeing processes.

Preference is given to dyeing, especially dyeing by the exhaust process.

The dyeing liquors or print pastes, in addition to water and the dyes,may contain further additives, for example wetting agents, antifoams,levelling agents or agents to influence the properties of the textilematerial, for example softeners, flame retardants or soil, water and oilrepellants, and also water softeners and natural or syntheticthickeners, for example alginates or cellulose ethers.

The amounts in which the dyes of the formula (I) are used in thedyebaths or print pastes can vary within wide limits, depending on thedesired depth of shade. Advantageous amounts will generally be in therange from 0.01% to 15% by weight and especially 0.1% to 10% by weight,based on the weight of fibre and based on the print paste, respectively.

The dyes of the formula (I) can likewise be used for mass coloration ofpolyester. The disperse dyes according to the invention can also firstbe processed into concentrates in which a polymer which is compatiblewith the polymer to be coloured serves as a carrier for the dispersedyes. The carrier material should belong to the same category ofpolymers or be a generally high-compatible substance. This avoidsadverse repercussions for the mechanical, thermal and opticalproperties. Such preparations contain the disperse dyes according to theinvention (or generally pigments and/or dyes) in highly concentratedform in a polymer-carrier adapted to the end product and which are usedfor mass coloration of polymers are customarily termed masterbatches.Alternatively, pellets or liquid formulations (dispersions) or simplydry blends can also be prepared for mass coloration of polymers.

The disperse dyes according to the invention are useful for pigmentingmacromolecular organic materials of natural or synthetic origin, forexample plastics, resins, coatings, paints, electrophotographic tonersand developers, colour filters and also inks, including printing inks.

The disperse dyes according to the invention are also useful ascolorants in aqueous and non-aqueous ink jet inks, microemulsion inksand also in such inks which are employed in the hot melt process.

Ink jet inks generally contain in total 0.5% to 15% by weight andpreferably 1.5% to 8% by weight (reckoned dry) of one or more of thedisperse dyes according to the invention.

Microemulsion inks are based on organic solvents, water and ifappropriate an additional hydrotropic substance (interface mediator).Microemulsion inks contain in general 0.5% to 15% by weight andpreferably 1.5% to 8% by weight of one or more of the disperse dyesaccording to the invention, 5% to 99% by weight of water and 0.5% to94.5% of organic solvent and/or hydrotropic compound.

“Solvent-based” ink jet inks contain preferably 0.5% to 15% by weight ofone or more of the disperse dyes according to the invention, 85% to99.5% by weight of organic solvent and/or hydrotropic compounds.

Hot-melt inks are usually based on waxes, fatty acids, fatty alcohols orsulphonamides which are solid at room temperature and become liquid onheating, the preferred melting range being situated between about 60° C.and about 140° C. Hot-melt ink jet inks consist essentially for exampleof 20% to 90% by weight of wax and 1% to 10% by weight of one or more ofthe disperse dyes according to the invention. There may further beincluded 0% to 20% by weight of an additional polymer (as“dye-dissolver”), 0% to 5% by weight of dispersing assistant, 0% to 20%by weight of viscosity modifier, 0% to 20% by weight of plasticizer, 0%to 10% by weight of tack additive, 0% to 10% by weight of transparencystabilizer (prevents crystallization of waxes, for example) and also 0%to 2% by weight of antioxidant.

Parts and percentages in the examples which follow are by weight. Thetemperatures are indicated in degrees Celsius.

EXAMPLE 1

16.3 parts of 2-cyano-4-nitroaniline are suspended in 100 parts of coldsulphuric acid 93% and admixed with 32 parts of nitrosylsulphuric acid(40%) at 0-5° C. in the course of 30 minutes. This is followed by 3-4hours of stirring at 0-5° C., and then the resulting diazonium saltsolution is poured continuously with stirring into a mixture of 29.7parts of phenylcarbonylmethyl 3-(N-methyl-N-phenylamino)-propionate, 100parts of glacial acetic acid, 2 parts of sulphamic acid, 200 parts ofwater and 300 parts of ice. The precipitated dye is filtered off, washedacid free with water and dried at 60° C. under reduced pressure. The dyeobtained conforms to the formula

It dyes polyester fibre material in ruby shades having excellentfastnesses, especially very good wet fastnesses after thermalstabilization, and is very useful, alone or in mixtures, for state ofthe art rapid-dyeing processes such as for example the ®Foron RDprocess. λ_(max)=530 nm (DMF)

EXAMPLE 2

26.2 parts of 2-bromo-4,6-dinitroaniline are suspended in 150 parts ofsulphuric acid 93% at 15-20° C. and admixed with 32 parts ofnitrosylsulphuric acid 40% in the course of 30 minutes. This is followedby 2-3 hours of stirring, and the diazonium salt solution is pouredcontinuously with stirring into a mixture of 36.8 parts ofphenylcarbonylmethyl3-(N-ethyl-N-(3′-acetylamino-phenylamino))-propionate, 100 parts ofglacial acetic acid, 2 parts of sulphamic acid, 100 parts of water and200 parts of ice. The precipitated dye is filtered off, washed acid freewith water and dried at 60° C. under reduced pressure. The dye obtainedconforms to the formula

and dyes polyester fibre material in violet shades having excellentfastnesses. The dye, which has λ_(max)=559 (DMF), is very useful, aloneor in navy or black mixtures, for state of the art rapid-dyeingprocesses such as for example the ®Foron RD process.

EXAMPLE 3

64.1 parts of 2-bromo-4,6-dinitroaniline-1-azo dye (preparationaccording to Example 2), 1 part of potassium iodide are suspended in 200parts of dimethyl sulphoxide at 60° C., admixed with 9.8 parts ofcopper(l) cyanide and stirred for 2-3 hours. The reaction product isfiltered off at about 50° C., washed with 50 parts of 1:1 DMSO / waterin portions and dried at 60° C. under reduced pressure. The dye obtainedconforms to the formula

and dyes polyester fibre material in blue shades having excellentfastnesses, especially having excellent wet fastnesses. The dye, whichhas λ_(max)=604 (DMF), is, alone or in mixtures, very useful for stateof the art rapid-dyeing processes such as for example the ®Foron RDprocess.

EXAMPLE 4

16.3 parts of 2-amino-4-chloro-5-formylthiazole are dissolved in 100parts of sulphuric acid 93% and admixed with 32 parts ofnitrosylsulphuric acid 40% at 0 to 5° C. in the course of 30 minutes.This is followed by 3 hours of stirring in an icebath, and the diazoniumsalt solution is poured continuously into a mixture of 41.0 parts ofphenylcarbonylmethyl3-[N-allyl-N-(5′-acetylamino-2′-methoxy-phenylamino)]-propionate, 100parts of glacial acetic acid, 2 parts of sulphamic acid and 300 parts ofice/water. The precipitated dye is filtered off, washed acid free withwater and dried at 60° C. under reduced pressure. The dye obtained,which has λ_(max)=625 (DMF), conforms to the formula

and dyes polyester materials in greenish navy shades and is useful asindividual dye or in navy and black mixtures for the ®Foron RDrapid-dyeing process, with very good fastnesses.

EXAMPLE 5

18.6 parts of 2-amino-4-chloro-3-cyano-5-formylthiophene are dissolvedin 200 parts of cold sulphuric acid 85%. 32 parts of nitrosylsulphuricacid 40% are added dropwise with stirring at 0 to 5° C. in the course of30 minutes. This is followed by 3 hours of stirring in an icebath, andthe diazonium salt solution is poured continuously into a mixture of32.5 parts of phenylcarbonylmethyl3-[N-ethyl-N-(3′-methylphenylamino)]-propionate, 50 parts of 5%sulphuric acid, 2 parts of sulphamic acid and 300 parts of ice. Theprecipitated dye is filtered off, washed acid free with water and driedat 60° C. under reduced pressure. The dye obtained having λ_(max)=610(DMF), conforms to the formula

and dyes polyester materials in brillant reddish blue shades having goodfastnesses.

Table 1 below indicates further dyes of the general formula (Ic); theyare prepared similarly to Examples 1 to 5.

and Table 2 subsequently indicates further dyes of the general formula(Id); they are prepared similarly to Examples 1 to 5.

TABLE 1 (dyes of the general formula (Ic)) λ_(max) Ex. (a) (b) (c) (d) YR¹ R² R³ R⁴ R⁵ (DMF) 6 NO₂ NO₂ H Br —C₂H₄— NHCOCH₃ H n-C₃H₇ H C₆H₅ 560 7NO₂ NO₂ H CN —C₂H₄— NHCOCH₃ H n-C₃H₇ H C₆H₅ 611 8 NO₂ NO₂ H CN —C₂H₄—NHCOC₂H₅ H C₂H₅ H C₆H₅ 612 9 NO₂ NO₂ H CN —C₂H₄— NHCOCH₃ H CH₂CH═CH₂ HC₆H₅ 608 10 NO₂ NO₂ H CN —C₂H₄— NHCOCH₃ H C₂H₄OCH₃ H C₆H₅ 609 11 NO₂ NO₂H CN —C₂H₄— NHCOCH₃ H CH₂CHOHCH₂Cl CH₃ C₆H₅ 608 12 NO₂ NO₂ H CN —C₂H₄—NHCOCH₂Cl H C₂H₅ H C₆H₅ 605 13 NO₂ NO₂ H CN —C₂H₄— NHCOCH₂CH₂Cl H C₂H₅ HC₆H₅ 607 14 CN NO₂ H CN —C₂H₄— NHCOCH₃ H n-C₄H₉ H CH₃ 615 15 CN NO₂ H CN—C₂H₄— NHCOCH₃ H n-C₃H₇ H C₂H₅ 614 16 CN NO₂ H CN —C₂H₄— NHCOCH₃ H C₂H₅H C₆H₅ 613 17 NO₂ NO₂ H CN —C₂H₄— NHCOCH₃ H CH₃ H C₆H₅ 610 18 NO₂ NO₂ HCN —C₂H₄— NHCOCH₃ H CH₂C(CH₃)H═CH₂ H C₆H₅ 612 19 NO₂ NO₂ H Cl —C₂H₄—NHCOCH₂OCH₃ OC₂H₅ H H C₆H₅ 596 20 NO₂ NO₂ H Cl —C₂H₄— NHCOCH₂Cl OCH₃ H HC₆H₅ 594 21 NO₂ NO₂ H Cl —C₂H₄— NHCOCH═CH₂ OCH₃ —C₆H₁₃ H C₆H₅ 608 22 NO₂NO₂ H Cl —C₂H₄— NHCHO OCH₃ CH₂C₆H₅ H C₆H₅ 602 23 NO₂ NO₂ H Cl —C₂H₄—NHCOCH₃ OCH₃ H H C₆H₅ 596 24 NO₂ NO₂ H Br —C₂H₄— NHCOCH₃ OCH₃ H H C₆H₅597 25 NO₂ NO₂ H Br —C₂H₄— NHCOCH₃ OCH₃ C₂H₄OCOCH₃ H C₆H₅ 591 26 NO₂ NO₂H J —C₂H₄— NHCOCH₃ OCH₃ C₂H₄OCH₃ H C₆H₅ 594 27 NO₂ NO₂ H CN —C₂H₄—NHCOCH₃ H CH₂CH₂CH₂Cl H C₆H₅ 609 28 NO₂ NO₂ H CN —CHCH₃CH₂— NHCOCH₃ HC₂H₄OC₂H₄OCH₃ H C₆H₅ 608 29 NO₂ NO₂ H CN —C₂H₄— NHCOCH₃ HCH₂CH₂CH₂CH₂OCOCH₃ H C₆H₅ 612 30 NO₂ NO₂ H CN —C₂H₄— NHCOCH₃ HCH₂CH(OCOCH₃)CH₃ H C₆H₅ 601 31 CN NO₂ H CN —C₂H₄— NHCOCH₃ H CH₂C₆H₅ HC₆H₅ 597 32 CN NO₂ H CN —C₂H₄— NHCOC₂H₅ H CH₂C₆H₅ H C₆H₅ 598 33 CN NO₂ HCN —C₂H₄— NHCOCH₃ OCH₃ CH₂C₆H₅ H C₆H₅ 635 34 NO₂ NO₂ H Br —C₂H₄— NHCOCH₃OCH₃ CH₂C₆H₅ H C₆H₅ 593 35 NO₂ NO₂ H Cl —C₂H₄— NHCOCH₃ OCH₃ CH₂C₆H₅ CH₃C₆H₅ 594 36 NO₂ NO₂ H Cl —(CH₂)₃— NHCOOCH₃ OCH₃ C₂H₄OCOCH₃ H C₆H₅ 591 37CN NO₂ H Br —C₂H₄— NHCOCH₃ H C₂H₅ H *—(CH₂)₃— 584 38 CN NO₂ H Br —C₂H₄—NHCOC₂H₅ H n-C₃H₇ H C₆H₅ 585 39 CN NO₂ H Cl —C₂H₄— NHCOCH₃ H C₂H₅ H C₆H₅584 40 CN NO₂ H H —C₂H₄— NHCOCH₃ H C₂H₅ H C₆H₅ 554 41 CN NO₂ H H—CHCH₃CH₂— NHCOCH₃ H C₂H₅ H C₆H₅ 555 42 CN NO₂ H H —C₂H₄— H H CH₂CH═CH₂H C₆H₅ 532 43 CN NO₂ H H —C₂H₄— H H CH₂C₆H₅ H C₆H₅ 530 44 CN NO₂ H H—C₂H₄— H H C₂H₄OC₆H₅ H C₆H₅ 534 45 Cl NO₂ H H —C₂H₄— NHCOCH₃ H CH₂CH═CH₂H C₆H₅ 527 46 Cl NO₂ H H —C₂H₄— NHCOCH₃ H CH₂COOC₂H₅ H C₆H₅ 517 47COOCH₃ NO₂ H H —C₂H₄— NHCOCH₃ H CH₂C₆H₅ H C₆H₅ 528 48 Cl NO₂ H H —C₂H₄—NHCOCH₃ H CH₂C₆H₅ H C₆H₅ 525 49 Cl SO₂CH₃ H H —C₂H₄— NHCOCH₃ H C₂H₅ HC₆H₅ 499 50 Cl NO₂ H H —C₂H₄— NHCOCH₃ Cl H H C₆H₅ 505 51 OH NO₂ H H—C₂H₄— NHCOCH₂OCH₃ H CH₂CH═CH₂ H C₆H₅ 520 52 OH NO₂ H H —C₂H₄— NHCOCH₃ HCH₂C₆H₅ H C₆H₅ 516 53 OH NO₂ H H —C₂H₄— H H C₂H₅ H C₆H₅ 518 54 CN Br HCN —C₂H₄— OH H C₂H₄OCOCH₂COC₆H₅ H C₆H₅ 510 55 CN CH3 H CN —C₂H₄— NHCOCH₃H CH₂C₆H₅ H C₆H₅ 526 56 H NO₂ H H —C₂H₄— H Cl H H C₆H₅ 450 57 H NO₂ H H—C₂H₄— NHCOCH₃ H C₂H₅ H *—(CH₂)₄— 514 58 H NO₂ H H —C₂H₄— NHCOCH₃ HCH₂C₆H₅ H C₆H₅ 507 59 NO₂ NO₂ SCN H —C₂H₄— CH₃ OCH₃ H H C₆H₅ 601 60 NO₂NO₂ SCN H —C₂H₄— NHCOCH₃ OCH₃ H H C₆H₅ 621

TABLE 2 (dyes of the general formula (Id)) Ex. D Y R¹ R² R³ R⁴ R⁵λ_(max)(DMF) 61 4-Chloro-5-formylthiazolyl-2 —C₂H₄— H H C₂H₅ H C₆H₅ 56362 4-Chloro-5-formylthiazolyl-2 —C₂H₄— CH₃ H C₂H₅ H C₆H₅ 586 634-Chloro-5-formylthiazolyl-2 —C₂H₄— CH₃ OCH₃ CH₂CH═CH₂ H C₆H₅ 609 644-Chloro-5-formylthiazolyl-2 —C₂H₄— NHCOCH₃ OCH₃ CH₂C₆H₅ H C₆H₅ 622 654-Chloro-5-formylthiazolyl-2 —C₂H₄— NHCOCH₃ OCH₃ H H C₆H₅ 608 715-Nitro-thiazolyl-2 —C₂H₄— H H C₂H₅ H C₆H₅ 587 72 5-Nitro-thiazolyl-2—C₂H₄— CH3 H C₂H₅ H C₆H₅ 606 73 5-Nitro-thiazolyl-2 —C₂H₄— NHCOCH₃ OCH₃H H C₆H₅ 630 66 4-Chloro-3-cyano-5-formylthienyl-2 —C₂H₄— H H C₂H₅ HC₆H₅ 593 67 4-Chloro-3-cyano-5-formylthienyl-2 —C₂H₄— CH₃ H C₂H₅ H C₆H₅608 68 4-Chloro-3-cyano-5-formylthienyl-2 —C₂H₄— NHCOCH₃ H C₂H₅ CH₃ C₆H₅606 69 4-Chloro-3-cyano-5-formylthienyl-2 —C₂H₄— NHCOCH₃ OCH₃ H H C₆H₅630 70 4-Chloro-3-cyano-5-formylthienyl-2 —C₂H₄— NHCOCH₃ OCH₃ C₂H₅ HC₆H₅ 652 71 3,5-Dinitro-thienyl-2 —C₂H₄— NHCOCH₃ H C₂H₅ H C₆H₅ 633 723,5-Dinitro-thienyl-2 —C₂H₄— CH₃ H c₂H₅ H C₆H₅ 637 733,5-Dinitro-thienyl-2 —C₂H₄— H H C₂H₅ H C₆H₅ 625 744-Cyano-3-methyl-isothiazolyl-5 —C₂H₄— H H C₂H₅ H C₆H₅ 543 754-Cyano-3-methyl-isothiazolyl-5 —C₂H₄— NHCOCH₃ H CH₂CH═CHCl H C₆H₅ 54576 5-Ethylmercapto-1,3,4-thiadiazolyl-2 —C₂H₄— NHCOCH₃ H C₂H₅ H C₆H₅ 52077 5-Ethylmercapto-1,3,4-thiadiazolyl-2 —C₂H₄— CH₃ H C₂H₅ H C₆H₅ 518 785-Ethylmercapto-1,3,4-thiadiazolyl-2 —C₂H₄— H H C₂H₅ H C₆H₅ 513 79(5),6-,(7)-Dichlorobenzothiazolyl-2 —C₂H₄— H H C₂H₅ H C₆H₅ 535 80(5),6-,(7)-Dichlorobenzothiazolyl-2 —C₂H₄— CH₃ H CH₂CH═CH₂ H C₆H₅ 537 81(5),6-,(7)-Dichlorobenzothiazolyl-2 —C₂H₄— NHCOCH₃ H C₂H₄CN H C₆H₅ 53082 6-Nitro-benzothiazolyl-2 —C₂H₄— H H C₂H₅ H C₆H₅ 533 836-Methylsulphonyl-benzothiazolyl-2 —C₂H₄— H H C₂H₅ H C₆H₅ 529 845-Nitro-2,1-benzisothiazolyl-3 —C₂H₄— H H C₂H₅ H C₆H₅ 603 851-Cyanomethyl-4,5-dicyano-imidazolyl-2 —C₂H₄— CH₃ H C₂H₅ H C₆H₅ 525 863-Cyano-5-phenylazo-thienyl-2 —C₂H₄— H H C₂H₅ H C₆H₅ 615 874-Cyano-3-methyl-1-phenylpyrazolyl-5 —C₂H₄— NHCOCH₃ H CH₂CH═CHCl H C₆H₅528 88 4-Cyano-3-methyl-1-phenylpyrazolyl-5 —C₂H₄— NHCOCH₃ H CH₂CH═CH₂ HC₆H₅ 533 89 4-Cyano-1-benzyl-1,2,3-triazolyl-5 —C₂H₄— NHCOCH₃ H C₂H₅ HC₆H₅ 536 90 4-Cyano-1-benzyl-1,2,3-triazolyl-5 —C₂H₄— NHCOC₂H₅ HCH₂CH═CHCl H C₆H₅ 529

1. A disperse dy of the general foumula (I)

where D is a diazo component derived from a substituted or unsubstitutedaromatic amine, K is an aromatic radical of the formula K₁, K₂ or K₃

R₁ is hydrogen, chlorine, C₁₋₂-alkyl, C₁₋₂-alkoxy, hydroxyl oracylamino, R₂ is hydrogen, C₁₋₄-alkoxy, C₁₋₂-alkoxyethoxy, chlorine,bromine or combines with R₃ to form a group of the formula—*CH(CH₃)CH₂C(CH₃)₂— (* attached to the nucleus), R₃ is hydrogen,C₁₋₆-alkyl, C₃₋₄-alkenyl, chloro- or bromo-C₃₋₄-alkenyl, C₃₋₄-alkynyl,phenyl-C₁₋₃-alkyl, C₁₋₄-alkoxycarbonyl-C₁₋₃-alkyl,C₃₋₄-alkenyloxycarbonyl-C₁₋₃-alkyl, C₃₋₄-alkynyloxycarbonyl-C₁₋₃-alkyl,phenoxy-C₂₋₄-alkyl, halogen-, cyano-, C₁₋₄-alkoxy-,C₁₋₄-alkylcarbonyloxy- or C₁₋₄-alkoxycarbonyloxy-substituted C₂₋₄-alkyl,or a group of the formula —CH₂—CH(R₈)CH₂—R₉, R₄ is hydrogen orC₁₋₂-alkyl, R₅ is phenyl optionally substituted by one or twosubstituents selected from the group consisting of methyl, chlorine,bromine and nitro or combines with R₄ to form a c-pentanone orc-hexanone ring, R₆ is hydrogen or hydroxyl, R₇ is hydrogen or methyl,R₈ is hydroxyl or C₁₋₄-alkylcarbonyloxy, R₉ is chlorine, C₁₋₄-alkoxy,phenoxy, allyloxy or C₁₋₄-alkylcarbonyloxy, Y is C₁₋₃-alkylene, whereinR₃ is hydrogen when K is a radical of the formula K₂ or K₃, with thefollowing formula being excluded


2. A disperse dye according to claim 1, of formula (Ia)

where D₁ is 3-phenyl-1,2,4-thiadiazolyl or conforms to one of thefollowing formulae:

where (a) is hydrogen, chlorine, bromine, cyano, nitro-,C₁₋₄-alkoxycarbonyl, C₁₋₃-alkyl-sulphonyl, (b) is chlorine, bromine,nitro, methyl, C₁₋₂-alkylsulphonyl, C₁₋₄-alkylcarbonyl, aminosulphonyl,mono- or di-C₁₋₄alkylaminosulphonyl, phenylaminosulphonyl,C₁₋₄-alkoxycarbonyl, benzyloxycarbonyl,tetrahydrofurfuryl-2-oxycarbonyl, C₃₋₄-alkenyloxycarbonyl,C₃₋₄-alkynyloxycarbonyl, aminocarbonyl, mono- ordi-C₁₋₄-alkylaminocarbonyl, phenylaminocarbonyl or phenylazo, (c) ishydrogen or chlorine or when (d) is hydrogenm (c) is hydroxyl or rhodan,(d) is hydrogen, chlorine, bromine, hydroxyl or cyano, (e) is nitro,C₁₋₄-alkylcarbonyl, C₁₋₄-alkoxycarbonyl, cyano, aminocarbonyl, mono- ordi-C₁₋₄-alkylaminocarbonyl, (f) is hydrogen, chlorine, bromine,C₁₋₂-alkyl or phenyl, (g) is nitro, cyano, formyl, dicyanovinyl or agroup of the formula —CH═CH—NO₂, —CH═C(CN)CO—OC₁₋₄-alkyl, H₅C₆—N═N— or3- or 4—NO₂—C₆H₄—N═N—, (h) is cyano or C₁₋₄-alkoxycarbonyl, (i) isC₁₋₄-alkyl or phenyl, (j) is —CN, —CH═CH₂ or phenyl, (k) is C₁₋₄-alkyl,(l) is hydrogen, chlorine, bromine, cyano, rhodan, nitro,C₁₋₄-alkoxycarbonyl or di-C₁₋₄-alkylaminosulphonyl, (p) is hydrogen,chlorine or bromine, and (q) is C₁₋₄-alkyl orC₁₋₄-alkoxycarbonyl-C₁₋₄-alkyl, wherein the phenyl nuclei of thesesubstituents optionally have one or two substituents selected from thegroup consisting of chlorine, bromine, methyl and C₁₋₂-alkoxy, R′₁ ishydrogen, methyl, chlorine or acylamino, R′₂ is hydrogen, chlorine,C₁₋₂-alkoxy, C₁₋₂-alkoxyethoxy or combines with R₃ to form a group ofthe formula —CH(CH₃)CH₂C(CH₃)₂—, R₃ and R₅ are each as defined above,R′₄ is hydrogen or methyl, and Y is a group of the formula —CH₂CH₂— or—CH₂CH(CH₃)—.
 3. A disperse dye according to claim 1, of formula (Ib)

where D₂ is the residue of a diazo component of the formula2,6-dicyano-4-chloro-, 2,6-dicyano-4-bromo-, 2,6-dicyano-4-methyl-,2,6-dicyano-4-nitrophenyl, 2,4-dinitro-6-chloro-, 2,4-d initro-6-bromo-or 2,4-dinitro-6-cyanophenyl, 2-chloro-4-nitro-6-cyanophenyl,2-bromo-4-nitro-6-cyanophenyl, 2,4-dinitrophenyl,2,6-dichloro-4-nitrophenyl, 2,6-dibromo-4-nitrophenyl,2-chloro-4-nitro-6-bromophenyl, 2-chloro-4-nitrophenyl,2-cyano-4-nitrophenyl, 2,4-dinitro-5,6-dichlorophenyl,2,5-dichloro-4-nitrophenyl, 4-nitro-phenyl, 4-phenylazophenyl,4—C₁₋₄-alkoxycarbonylphenyl, 2—C₁₋₄-alkoxy-carbonyl-4-nitrophenyl,4-benzyloxycarbonylphenyl, 4-(tetrahydrofurfuryl-2′-oxycarbonyl)phenyl,3,5-dicyano-4-chloro-thienyl-2,3,5-dicyano-thienyl-2,3-cyano-5-nitro-thienyl-2,3-acetyl-5-nitro-thienyl-2, 3,5-dinitro-thienyl-2,3-(C₁₋₄-alkoxycarbonyl)-5-nitro-thienyl-2,5-phenylazo-3-cyano-thienyl-2, 5-phenylazo-3-cyano-4-methyl-thienyl-2,5-nitro-thiazolyl-2, 5-nitrobenzoiso-thiazolyl-3,3-methyl-4-cyano-isothiazolyl-5, 3-phenyl-1,2,4-thiadiazolyl-2,5-(C₁₋₂-alkylmercapto)-1,3,4-thiadiazolyl-2,3-(C₁₋₂-alkoxycarbonylethyl-mercapto)-1,2,4-thiadiazolyl-5,1-cyanomethyl-4,5-dicyano-imidazolyl-2, 6-nitrobenzothiazolyl-2,5-nitrobenzothiazolyl-2, 6-rhodanbenzothiazolyl-2,6-chlorobenzothiazolyl-2, (5),6,(7)-dichlorobenzothiazolyl-2, or of theformula

and B is oxygen or a group of the formula ═(CN)₂, ═CH—NO₂,═(CN)—COOC₁₋₄alkyl or ═(CN)—COOC₃₋₄alkenyl and the symbols R′₁, R′₂, R₃,R′₄, R₅ and Y are each as defined above.
 4. A process for preparing adye of the formula (I), according to claim 1, comprising the step ofcoupling a diazotized amine of the formula (II)D—NH₂   (II) with a compound of the formula (III)H—K   (III) wherein D and K are each as defined in claim
 1. 5. A methodfor dyeing or printing or both a hydrophobic fibrous material comprisingthe step of contacting at least one dye according to claim 1 with thehydrophobic fibrous material.
 6. A method for printing a hydrophobicfibrous material comprising the step of contacting at least one dyeaccording to claim 1 with the hydrophobic fibrous material with an inkjet printing device or a hot melt ink jet printing device.
 7. Acomposition comprising at least one dye according to claim
 1. 8. Afibrous material printed or dyed or both with at least one dye accordingto claim
 1. 9. A method according to claim 5 wherein the hydrophobicfibrous material is polyester, acetate, triacetate fiber or a mixturethereof.
 10. A disperse dye according to claim 2 wherein (a) ishydrogen, chlorine, cyano or nitro.
 11. A fibrous material printed ordyed or both by a process according to claim 1.